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Title: Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations

Abstract

Here, a library of linear and branched amphiphilic poly(ionic liquid)s based on hydrophobic cores and peripheral thermally sensitive shells was synthesized and studied with regard to their ability to form stimuli-responsive, organized assemblies in aqueous media. The thermally responsive derivatives of poly(ionic liquid)s were synthesized by neutralizing 32 terminal carboxyl groups of functionalized polyester cores by amine-terminated poly( N-isopropylacrylamide)s (PNIPAM) (50% and 100%). We observed that these hyperbranched poly(ionic liquid)s possessed a narrow low critical solution transition (LCST) window with LCST for hyperbranched compounds being consistently lower than that for linear PNIPAM containing counterparts. We found that the poly(ionic liquid)s form spherical micellar assemblies with diverse morphologies, such as micelles and their aggregates, depending on the terminal compositions with reduced sizes for hyperbranched poly(ionic liquid)s. Increasing temperature above LCST promoted formation of network-like aggregates, large vesicles, and spherical micelles. Moreover, all PNIPAM-terminated compounds exhibited distinct unimolecular prolate nanodomain morphology in contrast to common spherical domains of initial cores. We proposed a multilength scale organized morphology to describe the thermoresponsive poly(ionic liquid)s micellar assemblies and discussed their morphological transformations during phase transitions associated with changes in hydrophobic–hydrophilic balance of poly(ionic liquid)s with distinct hydrophobic cores and variable peripheral shells.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [3];  [2];  [4]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. National Academy of Sciences of Ukraine, Kyiv (Ukraine)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Taras Shevchenko National University of Kyiv, Kyiv (Ukraine)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1484126
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 13; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hyperbranched poly(ionic liquid)s; grafted PNIPAM macrocations; reversible micellar assembly; LCST thermal response

Citation Formats

Korolovych, Volodymyr F., Erwin, Andrew, Stryutsky, Alexandr, Lee, Hansol, Heller, William T., Shevchenko, Valery V., Bulavin, Leonid A., and Tsukruk, Vladimir V. Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.8b00845.
Korolovych, Volodymyr F., Erwin, Andrew, Stryutsky, Alexandr, Lee, Hansol, Heller, William T., Shevchenko, Valery V., Bulavin, Leonid A., & Tsukruk, Vladimir V. Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations. United States. doi:10.1021/acs.macromol.8b00845.
Korolovych, Volodymyr F., Erwin, Andrew, Stryutsky, Alexandr, Lee, Hansol, Heller, William T., Shevchenko, Valery V., Bulavin, Leonid A., and Tsukruk, Vladimir V. Mon . "Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations". United States. doi:10.1021/acs.macromol.8b00845. https://www.osti.gov/servlets/purl/1484126.
@article{osti_1484126,
title = {Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations},
author = {Korolovych, Volodymyr F. and Erwin, Andrew and Stryutsky, Alexandr and Lee, Hansol and Heller, William T. and Shevchenko, Valery V. and Bulavin, Leonid A. and Tsukruk, Vladimir V.},
abstractNote = {Here, a library of linear and branched amphiphilic poly(ionic liquid)s based on hydrophobic cores and peripheral thermally sensitive shells was synthesized and studied with regard to their ability to form stimuli-responsive, organized assemblies in aqueous media. The thermally responsive derivatives of poly(ionic liquid)s were synthesized by neutralizing 32 terminal carboxyl groups of functionalized polyester cores by amine-terminated poly(N-isopropylacrylamide)s (PNIPAM) (50% and 100%). We observed that these hyperbranched poly(ionic liquid)s possessed a narrow low critical solution transition (LCST) window with LCST for hyperbranched compounds being consistently lower than that for linear PNIPAM containing counterparts. We found that the poly(ionic liquid)s form spherical micellar assemblies with diverse morphologies, such as micelles and their aggregates, depending on the terminal compositions with reduced sizes for hyperbranched poly(ionic liquid)s. Increasing temperature above LCST promoted formation of network-like aggregates, large vesicles, and spherical micelles. Moreover, all PNIPAM-terminated compounds exhibited distinct unimolecular prolate nanodomain morphology in contrast to common spherical domains of initial cores. We proposed a multilength scale organized morphology to describe the thermoresponsive poly(ionic liquid)s micellar assemblies and discussed their morphological transformations during phase transitions associated with changes in hydrophobic–hydrophilic balance of poly(ionic liquid)s with distinct hydrophobic cores and variable peripheral shells.},
doi = {10.1021/acs.macromol.8b00845},
journal = {Macromolecules},
number = 13,
volume = 51,
place = {United States},
year = {2018},
month = {6}
}

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